JP6405874B2 - Resin composition containing polyamide polyester and adhesive - Google Patents

Description

  The present invention relates to a resin composition containing a polyamide polyester and an adhesive, and further relates to a multilayer film having the adhesive as an adhesive layer.

  Packaging materials typically used for packaging foods and beverages protect the contents from various distributions, storage such as refrigeration and processing such as heat sterilization, so that the strength, resistance to cracking, retort resistance, heat resistance In addition to functions such as sexuality, a wide variety of functions are required, such as excellent transparency so that the contents can be confirmed.

  On the other hand, when the bag is sealed by heat sealing, an unstretched polyolefin film having excellent heat processability is essential, but the unstretched polyolefin film has many functions that are insufficient as a packaging material. In particular, high barrier properties are required for the purpose of maintaining the quality of the contents and maintaining the content. Such a barrier packaging material is usually used as a composite flexible film in which different polymer materials and inorganic materials are laminated.

  When imparting a barrier function to a multilayer film, it is difficult to impart the barrier function to the unstretched polyolefin films used for the inner layer (sealant side) by coating or vapor deposition. Therefore, a barrier function is often imparted to various films (polyester resins such as polyethylene terephthalate (hereinafter abbreviated as PET), polyamide resins, stretched polyolefin resins) used on the outer layer side.

When a barrier function is imparted to these outer layer side films by coating, as the barrier coating material, vinylidene chloride having a high retort resistance and gas or water vapor barrier property has been frequently used, but dioxins are generated at the time of disposal firing, etc. There is a problem. Further, when a polyvinyl alcohol resin or an ethylene-polyvinyl alcohol copolymer is used as a barrier coating material, the gas barrier property is high, but there is a problem that the water vapor barrier property is remarkably lowered. Further, a film provided with a vapor deposition layer of a metal oxide such as silica or alumina as a gas barrier layer is expensive and has poor flexibility, and there is a problem that gas barrier performance varies due to cracks and pinholes.
As described above, in order to provide a barrier function, there are problems such as using a material that has a large impact on the environment, or using an expensive vapor deposition film, and providing a material that has an excellent barrier function. It is requested.

  Patent Document 1 discloses a two-part curable polyurethane resin composition having high gas barrier properties and high adhesive properties, in particular, excellent adhesive performance to various polymers, paper, metal, etc. after boil / retort treatment, and this A gas barrier laminate adhesive comprising a two-component curable polyurethane resin composition comprising a component (A) comprising an active hydrogen-containing compound as a main component and a component (B) comprising an organic polyisocyanate compound as a main component, The active hydrogen-containing compound is at least one compound selected from an alkylene oxide adduct of an araliphatic polyamine, a polyol adduct of an araliphatic polyisocyanate compound, and an araliphatic polyol, (A) and (B) A specific skeleton structure is contained in the cured resin formed by the reaction of 20% by weight or more. Two-part curable polyurethane resin composition is described.

Patent Document 2 discloses a laminating adhesive having high gas barrier properties and suitable adhesion to film materials such as various polymers, paper, and metal, and a laminating film, multilayer packaging material and packaging using the same. Regarding the bag, an epoxy resin and a reaction product of the following (A) and (B) having a specific structure or an epoxy resin curing agent which is a reaction product of (A), (B) and (C) An adhesive for laminating comprising a resin composition as a main component, wherein the epoxy resin cured product formed from the epoxy resin composition contains 40% by weight or more of a skeleton structure represented by the formula (1) Characteristic laminating adhesive.
(A) a polyfunctional compound having at least one acyl group that can form an amide group site by reaction with meta-xylenediamine or para-xylenediamine (B) polyamine (C) having 1 to 8 carbon atoms Monovalent carboxylic acid and / or its derivative

Patent Document 3 includes a polyvalent carboxylic acid component containing at least one ortho-oriented aromatic dicarboxylic acid or an anhydride thereof, ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol. An amorphous polyester polyol obtained by polycondensation of a polyhydric alcohol component containing at least one selected from the group;
A gas barrier film containing a curing agent capable of reacting with the gas barrier film is used, and a gas barrier film characterized by having a gas barrier property by a layer obtained by the adhesive is described in this document. In the described invention, a polyester polyol resin having no amide structure is used.

Japanese Patent No. 4092549 Japanese Patent No. 4366563 Japanese Patent No. 49626666

In the prior art, there is no example using the resin composition containing the polyamide polyester which is the object of the present invention as an adhesive having gas barrier properties.
Then, the subject of this invention provides the resin composition containing the polyamide polyester which has not existed before, and since the said resin composition is excellent in gas barrier property, the adhesive for gas barrier materials using the said resin composition is provided. The task is to do.
Furthermore, it is an object of the present invention to provide a gas barrier material that is excellent in gas barrier properties and can cope with the environment, which has been difficult to overcome by conventional techniques, by providing a multilayer film using the adhesive.
Another object is to provide a method for producing the polyamide polyester.

  In the present invention, at least one dicarboxylic acid selected from the group consisting of isophthalic acid, orthophthalic acid, and phthalic anhydride, an aliphatic dicarboxylic acid having 3 to 5 carbon atoms, an aliphatic diol having 2 to 4 carbon atoms, carbon The above-mentioned problems are solved by providing a resin composition containing a polyamide polyester obtained by polycondensation of amino alcohols of 2 to 4.

According to the present invention, it is possible to provide an adhesive for a gas barrier material using a resin composition containing an unprecedented polyamide polyester.
Furthermore, by providing a multilayer film using the adhesive, it is possible to provide a gas barrier material that is excellent in gas barrier properties and can cope with the environment.

The present invention comprises the following items.
1. At least one dicarboxylic acid selected from the group consisting of isophthalic acid, orthophthalic acid, and phthalic anhydride, an aliphatic dicarboxylic acid having 3 to 5 carbon atoms, an aliphatic diol having 2 to 4 carbon atoms, and 2 to 4 carbon atoms A resin composition containing a polyamide polyester obtained by polycondensation of an amino alcohol,
2. 1. An aliphatic dicarboxylic acid having 3 to 5 carbon atoms is succinic acid. The resin composition according to
3. 1. The aliphatic diol having 2 to 4 carbon atoms is ethylene glycol. Or 2. The resin composition according to
4). 1. Amino alcohol having 2 to 4 carbon atoms is 2-aminoethyl alcohol ~ 3. The resin composition according to any one of
5. Further, it contains an isocyanate compound. ~ 4. The resin composition according to any one of
6). 1. The isocyanate compound contains a polyisocyanate having an aromatic ring. ~ 5. The resin composition according to any one of the above.
7). 5. Polyisocyanate having an aromatic ring is a reaction product of metaxylene diisocyanate or metaxylene diisocyanate and an alcohol having two or more hydroxyl groups. The resin composition according to
8.1. ~ 7. An adhesive for gas barrier materials using the resin composition according to any one of
9.8. A multilayer film having an adhesive for gas barrier material according to claim 1, as an adhesive layer,
10.9. A packaging material using the multilayer film according to claim 1,
11. At least one dicarboxylic acid selected from the group consisting of isophthalic acid, orthophthalic acid, and phthalic anhydride, an aliphatic dicarboxylic acid having 3 to 5 carbon atoms, an aliphatic diol having 2 to 4 carbon atoms, and 2 to 4 carbon atoms In the method for producing a polyamide polyester obtained by polycondensation of amino alcohol,
An aliphatic group having 3 to 5 carbon atoms after polycondensation of at least one dicarboxylic acid selected from the group consisting of isophthalic acid, orthophthalic acid and phthalic anhydride with an amino alcohol having 2 to 4 carbon atoms A process for producing a polyamide polyester comprising polycondensing a dicarboxylic acid and an aliphatic diol having 2 to 4 carbon atoms.

Details will be described below.
The polyamide polyester of the present invention includes at least one dicarboxylic acid selected from the group consisting of isophthalic acid, orthophthalic acid, and phthalic anhydride, an aliphatic dicarboxylic acid having 3 to 5 carbon atoms, and an aliphatic having 2 to 4 carbon atoms. It is characterized by polycondensation of diol and amino alcohol having 2 to 4 carbon atoms.
More specifically, as the aliphatic dicarboxylic acid having 3 to 5 carbon atoms, malonic acid, succinic acid, glutaric acid and the like, and as the aliphatic diol having 2 to 4 carbon atoms, more specifically, Ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and the like. More specifically, examples of the alcohol include aminoethyl alcohol, aminopropyl alcohol, aminobutyl alcohol and the like.
Among these, it is particularly preferable to use succinic acid as the aliphatic dicarboxylic acid, ethylene glycol as the aliphatic diol, and 2-aminoethyl alcohol as the amino alcohol because of excellent barrier properties.

  The polyamide polyester of the present invention can be obtained by polycondensation using the above-mentioned raw materials by a known and usual method, and general production conditions include dehydration polycondensation reaction between 170-200 ° C. Can do. The reaction atmosphere may be under a nitrogen stream or the polycondensation reaction may be promoted by reducing the pressure.

  Further, in the method for producing a polyamide polyester of the present invention, in order for the adhesive obtained from the resin composition containing the polyamide polyester to exhibit stronger gas barrier properties, from the group consisting of isophthalic acid, orthophthalic acid, and phthalic anhydride. After polycondensation of at least one selected dicarboxylic acid and an amino alcohol having 2 to 4 carbon atoms, an aliphatic dicarboxylic acid having 3 to 5 carbon atoms, an aliphatic diol having 2 to 4 carbon atoms, and May be polycondensed. It is preferable to carry out the production in the order of this step because a resin composition having more excellent solvent solubility and barrier properties can be obtained.

The resin composition of the present invention may contain an isocyanate compound as a curing agent.
The curing agent used in the present invention is not particularly limited as long as it is an isocyanate compound that can react with the hydroxyl group of the resin composition, and examples thereof include a diisocyanate compound and a polyisocyanate compound, and an epoxy compound is also used. Is possible. Especially, it is preferable to use a polyisocyanate compound from a viewpoint of adhesiveness or retort resistance.

  Polyisocyanate compounds include aromatic and aliphatic diisocyanates and trivalent or higher polyisocyanate compounds, which may be either low molecular compounds or high molecular compounds. For example, tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, or a trimer of these isocyanate compounds, and an excess amount of these isocyanate compounds For example, ethylene glycol, propylene glycol, metaxylene alcohol, 1,3-bishydroxyethylbenzene, 1,4-bishydroxyethylbenzene, trimethylolpropane, glycerol, pentaerythritol, erythritol, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, tri Ethanol , Low molecular weight active hydrogen compounds such as metaxylene diamine and alkylene oxide adducts thereof, various polyester resins, polyether polyols, polymeric active hydrogen compound such as reacted with the resulting adduct of polyamides and the like.

  The isocyanate compound may be a blocked isocyanate. As the isocyanate blocking agent, for example, phenols such as phenol, thiophenol, methylthiophenol, ethylthiophenol, cresol, xylenol, resorcinol, nitrophenol, chlorophenol, acetoxime, methyl ethyl ketoxime, cyclohexanone oxime oximes, methanol, Alcohols such as ethanol, propanol and butanol; halogen-substituted alcohols such as ethylene chlorohydrin and 1,3-dichloro-2-propanol; tertiary alcohols such as t-butanol and t-pentanol; Examples include lactams such as caprolactam, δ-valerolactam, γ-butyrolactam, β-propylolactam, and other aromatic amines, imides, acetylacetate. , Acetoacetic ester, active methylene compounds such as malonic acid ethyl ester, mercaptans, imines, ureas, and also such as diaryl compounds sodium bisulfite. The blocked isocyanate can be obtained by subjecting the above isocyanate compound and the isocyanate blocking agent to an addition reaction by a known and appropriate method.

  Of these, xylene diisocyanate, hydrogenated xylene diisocyanate, toluene diisocyanate, and diphenylmethane diisocyanate are preferred, and metaxylene diisocyanate is most preferred in order to obtain good gas barrier properties. A polyisocyanate compound containing a meta-xylene skeleton is preferable because the gas barrier property can be improved not only by hydrogen bonding of a urethane group but also by π-π stacking of aromatic rings.

  The glass transition temperature of the cured coating film of the resin composition of the present invention and the isocyanate compound is preferably in the range of −30 ° C. to 80 ° C. More preferably, it is 0 degreeC-70 degreeC. More preferably, it is 25 degreeC-70 degreeC. When the glass transition temperature is higher than 80 ° C., the flexibility of the cured coating film near room temperature becomes low, and thus the adhesiveness to the substrate may be deteriorated due to poor adhesion to the substrate. On the other hand, when the temperature is lower than −30 ° C., there is a fear that sufficient gas barrier properties may not be obtained due to intense molecular motion of the cured coating film at around room temperature, and there is a risk that adhesive strength may be reduced due to insufficient cohesive force.

  Moreover, when carboxylic acid remains at the terminal of the resin composition used in the present invention, an epoxy compound can be used as a curing agent. Examples of epoxy compounds include diglycidyl ether of bisphenol A and oligomers thereof, diglycidyl ether of hydrogenated bisphenol A and oligomers thereof, orthophthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, and p-oxybenzoic acid diglyceride. Glycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, succinic acid diglycidyl ester, adipic acid diglycidyl ester, sebacic acid diglycidyl ester, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1 , 4-Butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether and polyalkylene glycol Cole diglycidyl ethers, trimellitic acid triglycidyl ester, triglycidyl isocyanurate, 1,4-diglycidyloxybenzene, diglycidyl propylene urea, glycerol triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether , Pentaerythritol tetraglycidyl ether, triglycidyl ether of glycerol alkylene oxide adduct, and the like.

  When an epoxy compound is used as a curing agent, a general-purpose known epoxy curing accelerator may be appropriately added for the purpose of accelerating curing within a range that does not impair the gas barrier property that is the object of the present invention.

  Examples of the polyisocyanate compound containing a meta-xylene skeleton include a trimer of xylene diisocyanate, a burette synthesized by reaction with an amine, and an adduct obtained by reacting with an alcohol. The adduct is more preferable because the solubility of the polyisocyanate compound in the organic solvent used for the dry laminate adhesive is easily obtained. As the adduct, an adduct obtained by reacting with an alcohol appropriately selected from the above low molecular active hydrogen compounds can be used. Among them, addition of ethylene oxide of trimethylolpropane, glycerol, triethanolamine, metaxylenediamine, etc. Adduct bodies with objects are particularly preferred.

  In the resin composition and the curing agent, the ratio of the resin composition and the curing agent is such that the hydroxyl group of the resin composition and the reaction component of the curing agent are 1 / 0.5 to 1/10 (equivalent ratio). It is preferable to mix | blend with, More preferably, it is 1 / 1-1 / 5. If the curing agent component is excessive beyond this range, the excess curing agent component may be left out and bleed out from the adhesive layer after bonding. On the other hand, if the curing agent component is insufficient, the adhesive strength is insufficient. There is a fear.

  The said hardening | curing agent can also use together the well-known hardening | curing agent or accelerator selected according to the kind. Examples of the adhesion promoter include silane coupling agents such as hydrolyzable alkoxysilane compounds, titanate coupling agents, aluminum coupling agents, and epoxy resins. Silane coupling agents and titanate coupling agents are also preferred in terms of improving the adhesive to various film materials.

  The adhesive of this invention may mix | blend various additives in the range which does not impair gas barrier property. Examples of additives include inorganic fillers such as silica, alumina, mica, talc, aluminum flakes, and glass flakes, layered inorganic compounds, stabilizers (antioxidants, heat stabilizers, ultraviolet absorbers, etc.), plasticizers, Examples thereof include an antistatic agent, a lubricant, an antiblocking agent, a colorant, a filler, and a crystal nucleating agent. Examples of swellable inorganic layered compounds include hydrous silicates (phyllosilicate minerals, etc.), kaolinite group clay minerals (halloysite, kaolinite, enderite, dickite, nacrite, etc.), antigolite group clay minerals (anti Golite, chrysotile, etc.), smectite clay mineral (montmorillonite, beidellite, nontronite, saponite, hectorite, soconite, stevensite, etc.), vermiculite clay mineral (vermiculite, etc.), mica or mica clay mineral (white mica, Mica such as phlogopite, margarite, tetrasilic mica, teniolite, etc.). These minerals may be natural clay minerals or synthetic clay minerals. The swellable inorganic layered compounds are used alone or in combination of two or more.

  Moreover, as a method for improving the acid resistance of the adhesive layer, a known acid anhydride can be used in combination as an additive. Examples of the acid anhydride include phthalic acid anhydride, succinic acid anhydride, het acid anhydride, hymic acid anhydride, maleic acid anhydride, tetrahydrophthalic acid anhydride, hexahydraphthalic acid anhydride, tetraprom phthalic acid Anhydride, tetrachlorophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenotetracarboxylic anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 5- (2 , 5-oxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, styrene maleic anhydride copolymer and the like.

  Moreover, you may add the compound etc. which have an oxygen trap function further as needed. Examples of the compound having an oxygen scavenging function include low molecular organic compounds that react with oxygen such as hindered phenols, vitamin C, vitamin E, organic phosphorus compounds, gallic acid, pyrogallol, cobalt, manganese, nickel, iron, Examples include transition metal compounds such as copper.

  Moreover, in order to improve the adhesiveness with respect to various film materials immediately after application | coating, you may add tackifiers, such as a xylene resin, a terpene resin, a phenol resin, and a rosin resin, as needed. When adding these, the range of 0.01-5 mass parts is preferable with respect to 100 mass parts of total amounts of an epoxy resin and an epoxy resin hardening | curing agent.

The adhesive of the present invention may be either a solvent type or a solventless type. In the case of the solvent type, the solvent may be used as a reaction medium during the production of the polyester polyol and the curing agent.
Furthermore, it is used as a diluent during painting. Examples of solvents that can be used include esters such as ethyl acetate, butyl acetate and cellosolve acetate, ketones such as acetone, methyl ethyl ketone, isobutyl ketone and cyclohexanone, ethers such as tetrahydrofuran and dioxane, and aromatic hydrocarbons such as toluene and xylene. , Halogenated hydrocarbons such as methylene chloride and ethylene chloride, dimethyl sulfoxide, dimethyl sulfoamide and the like. Of these, it is usually preferable to use ethyl acetate or methyl ethyl ketone.

  In addition, when used without a solvent, it is not always necessary to be soluble in an organic solvent, but considering the washing of a reaction kettle during synthesis and the washing of a coating machine during lamination, Sex is necessary.

  The adhesive of the present invention can be used by being applied to a substrate film or the like. The coating method is not particularly limited and may be performed by a known method. For example, in the case of a solvent type whose viscosity can be adjusted, it is often applied by a gravure roll coating method or the like. Moreover, when it is a solventless type and has a high viscosity at room temperature and is not suitable for gravure roll coating, it can be coated with a roll coater while heating. When using a roll coater, it is preferable to apply in a state of heating from room temperature to about 120 ° C. so that the viscosity of the adhesive of the present invention is about 500 to 2500 mPa · s.

The adhesive of the present invention can be used as an adhesive having gas barrier properties for various applications that require gas barrier properties against polymers, paper, metals, and the like.
Hereinafter, an adhesive for film lamination will be described as one of specific applications.

  The adhesive of the present invention can be used as an adhesive for film lamination. Since the laminated multilayer film is excellent in gas barrier properties, it can be used as a multilayer film for gas barrier materials.

  The film for lamination used in the present invention is not particularly limited, and a thermoplastic resin film can be appropriately selected according to a desired application. For example, for food packaging, PET film, polystyrene film, polyamide film, polyacrylonitrile film, polyethylene film (LLDPE: low density polyethylene film, HDPE: high density polyethylene film) and polypropylene film (CPP: unstretched polypropylene film, OPP: Polyolefin film such as biaxially stretched polypropylene film), polyvinyl alcohol film, ethylene-vinyl alcohol copolymer film, and the like. These may be subjected to stretching treatment. As a stretching treatment method, it is common to perform simultaneous biaxial stretching or sequential biaxial stretching after a resin is melt-extruded by extrusion film forming method or the like to form a sheet. Further, in the case of sequential biaxial stretching, it is common to first perform longitudinal stretching and then perform lateral stretching. Specifically, a method of combining longitudinal stretching using a speed difference between rolls and transverse stretching using a tenter is often used.

  Moreover, you may perform various surface treatments, such as a flame treatment and a corona discharge treatment, as needed so that the adhesive layer without defects, such as a film | membrane piece and a repellency, may be formed in the film surface.

  After the adhesive of the present invention is applied to one of the thermoplastic resin films, the other thermoplastic resin film is stacked and bonded together by lamination to obtain the multilayer film for a gas barrier material of the present invention. As the lamination method, known lamination such as dry lamination, non-solvent lamination, extrusion lamination, etc. can be used.

Specifically, in the dry lamination method, the adhesive of the present invention is applied to one of the base films by the gravure roll method, and the other base film is stacked and bonded by dry lamination (dry lamination method). The temperature of the laminate roll is preferably about room temperature to 60 ° C.
In addition, non-solvent lamination is applied to the substrate film with a roll such as a roll coater heated to room temperature to 120 ° C., and then immediately applied to the surface after the adhesive of the present invention, which has been heated to room temperature to 120 ° C. in advance, is applied. A laminate film can be obtained by laminating various film materials. The laminating pressure is preferably about 10 to 300 kg / cm ² .

  In the case of the extrusion laminating method, the organic solvent solution of the adhesive of the present invention is applied to the base film as a bonding aid (anchor coating agent) with a roll such as a gravure roll, and the solvent is dried and cured at room temperature to 140 ° C. After the reaction, a laminate film can be obtained by laminating the polymer material melted by the extruder. The polymer material to be melted is preferably a polyolefin resin such as a low density polyethylene resin, a linear low density polyethylene resin, or an ethylene-vinyl acetate copolymer resin.

  Moreover, it is preferable that the multilayer film for gas barrier materials of this invention performs aging after preparation. If polyisocyanate is used as a curing agent, the aging condition is from room temperature to 80 ° C., for 12 to 240 hours, during which adhesive strength is generated.

  In the present invention, in order to give a higher barrier function, a film in which a vapor-deposited layer of a metal such as aluminum or a metal oxide such as silica or alumina is laminated, polyvinyl alcohol, or ethylene / vinyl alcohol as necessary. A barrier film containing a gas barrier layer such as a polymer or vinylidene chloride may be used in combination.

  The adhesive of the present invention can be preferably used as an adhesive for a multilayer film formed by bonding a plurality of the same or different resin films. The resin film may be appropriately selected depending on the purpose. For example, when used as a packaging material, the outermost layer is a thermoplastic resin film selected from PET, OPP, and polyamide, and the innermost layer is unstretched polypropylene. (Hereinafter abbreviated as CPP), low-density polyethylene film (hereinafter abbreviated as LLDPE), a two-layer composite film using a thermoplastic resin film, or an outermost layer selected from, for example, PET, polyamide, and OPP A three-layer composite using a thermoplastic resin film, a thermoplastic resin film that forms an intermediate layer selected from OPP, PET, and polyamide, and a thermoplastic resin film that forms an innermost layer selected from CPP and LLDPE Form an outermost layer selected from a film, for example, OPP, PET, polyamide Selected from a thermoplastic resin film, a thermoplastic film forming a first intermediate layer selected from PET and nylon, a thermoplastic film forming a second intermediate layer selected from PET and polyamide, LLDPE, and CPP A composite film composed of four layers using a thermoplastic resin film forming the innermost layer can be preferably used as a food packaging material as an oxygen and water vapor barrier film.

Since the adhesive of the present invention is characterized by having a high gas barrier property, the laminate film formed by the adhesive is a PVDC coat layer, a polyvinyl alcohol (PVA) coat layer, an ethylene-vinyl alcohol copolymer ( EVOH) film layer, meta-xylene adipamide film layer, and a gas barrier property of a very high level is developed without using a commonly used gas barrier material such as an inorganic vapor deposition film layer on which alumina or silica is deposited.
Moreover, the gas barrier property of the obtained film can also be remarkably improved by using together as an adhesive agent which bonds these conventional gas barrier material and sealant material together.

  Next, the present invention will be specifically described with reference to examples and comparative examples. Unless otherwise indicated, “part” and “%” are based on mass.

(Production Example 1) Production of polyamide polyester polyol SIEA-1 obtained by polycondensation of isophthalic acid, succinic acid, ethylene glycol, and aminoethyl alcohol In a reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a rectification tube, a water separator, etc. Then, 113.1 parts of isophthalic acid and 82.3 parts of aminoethyl alcohol were charged and heated to 70 ° C. while flowing nitrogen. At that time, when an exothermic reaction occurred and the temperature in the container was increased to 170 ° C, the temperature was further increased to 200 ° C. Here, after confirming that a theoretical amount of water was generated, the temperature was lowered to 100 ° C., 120.6 parts of succinic acid, 54.1 parts of ethylene glycol, and 0.024 part of titanium tetraisopropoxide as a catalyst. Was heated gradually so that the upper temperature of the rectifying tube did not exceed 100 ° C., and the internal temperature was maintained at 200 ° C. for 7 hours. Thereafter, the pressure was reduced at the same temperature for 2.5 hours. When the acid value became 1 mgKOH / g or less, the esterification reaction was terminated, and a polyamide polyester polyol SIEA-1 having a number average molecular weight of 800 was obtained.

(Production Example 2) Production of polyamide polyester polyol SIEA-2 obtained by polycondensation of isophthalic acid, succinic acid, ethylene glycol, and aminoethyl alcohol. Production Example 1 is the same as Production Example 1 except that the amounts of various monomers are different. A polyamide polyester polyol SIEA-2 having a number average molecular weight of 800 was obtained. The monomers used in the synthesis were 244.8 parts of isophthalic acid, 137.2 parts of aminoethyl alcohol, 261.1 succinic acid, and 167.3 parts of ethylene glycol.

(Production Example 3) Production of polyamide polyester polyol SIEA-3 obtained by polycondensation of isophthalic acid, succinic acid, ethylene glycol, and aminoethyl alcohol. Production Example 1 is the same as Production Example 1 except that the amounts of various monomers are different. A polyamide polyester polyol SIEA-3 having a number average molecular weight of 800 was obtained. The monomers used in the synthesis were 112.9 parts isophthalic acid, 82.9 parts aminoethyl alcohol,
Succinic acid 120.4, ethylene glycol 42.2 parts.

(Production Example 4) Production of Polyamide Polyester Polyol SOEA-4 Polycondensed Orthophthalic Acid, Succinic Acid, Ethylene Glycol, and Aminoethyl Alcohol Production Example 1 uses orthophthalic acid instead of isophthalic acid, and other A polyamide polyester polyol SOEA-4 having a number average molecular weight of 800 was obtained in the same manner as in Production Example 1 except that the amounts of various monomers were different. The monomers used in the synthesis were 244.0 parts orthophthalic acid, 134.5 parts aminoethyl alcohol, 260.2 succinic acid, and 136.7 parts ethylene glycol.

(Production Example 5) Production of polyamide polyester polyol SOEA-5 obtained by polycondensation of phthalic anhydride, succinic acid, ethylene glycol, and aminoethyl alcohol Production Example 1 used phthalic anhydride instead of isophthalic acid, A polyamide polyester polyol SOEA-5 having a number average molecular weight of 1000 was obtained in the same manner as in Production Example 1 except that the amounts of various other monomers were different. The monomers used in the synthesis were 101.0 parts of phthalic anhydride, 54.1 parts of aminoethyl alcohol, 120.6 succinic acid, and 54.1 parts of ethylene glycol.

(Production Example 6) Production of polyamide polyester polyol AIEA-6 obtained by polycondensation of isophthalic acid, adipic acid, ethylene glycol, and aminoethyl alcohol Production Example 1 used adipic acid instead of succinic acid, and other A polyamide polyester polyol AIEA-6 having a number average molecular weight of 650 was obtained in the same manner as in Production Example 1 except that the amounts of various monomers were different. The monomers used in the synthesis were 237.4 parts of isophthalic acid, 172.6 parts of aminoethyl alcohol, 313.9 parts of adipic acid, and 112.8 parts of ethylene glycol.

(Production Example 7) Production of polyamide polyester polyol SIPA-7 obtained by polycondensation of isophthalic acid, succinic acid, polyethylene glycol, and aminoethyl alcohol Production Example 1 used polyethylene glycol 200 instead of ethylene glycol, and other than this A polyamide polyester polyol SIPA-7 having a number average molecular weight of 900 was obtained in the same manner as in Production Example 1 except that the amounts of these various monomers were different. The monomers used in the synthesis were 122.4 parts of isophthalic acid, 83.6 parts of aminoethyl alcohol, 71.0 parts of succinic acid, and 54.5 parts of polyethylene glycol.

(Production Example 8) Production of polyamide polyester polyol SIEH-8 obtained by polycondensation of isophthalic acid, succinic acid, ethylene glycol, and hexamethylene diamine Production Example 1 was obtained by using hexamethylene diamine instead of aminoethyl alcohol, and this A polyamide polyester polyol SIEH-8 having a number average molecular weight of 460 was obtained in the same manner as in Production Example 1 except that the amounts of various monomers other than were different. The monomers used in the synthesis were 498 parts isophthalic acid, 116.2 parts hexamethylenediamine, 118.0 succinic acid, and 279 parts ethylene glycol.

(Summary of monomer composition of resin)
As mentioned above, it shows in Table 1 about the usage-amount of various resin raw material monomers shown to manufacture examples 1-8.

(Adhesive compounding in Examples and Comparative Examples 1 to 3)
Table 2 shows the formulation when the resins obtained in Production Examples 1 to 5 are made into adhesives as examples.
In addition, Table 3 shows the composition when the resins obtained in Production Examples 6 to 8 are made into adhesives as comparative examples. At this time, in all examples and comparative examples, first, according to the composition of the table, various resins were dissolved in 2-butanone (methyl ethyl ketone) at room temperature by stirring with a stirrer, and a procedure for adding a curing agent to those that could be completely dissolved was performed. I took it. The dissolved state at this time is also shown in Tables 2 and 3. Since the resin that could not be completely dissolved at this time cannot be used as a dry lamination type adhesive, the curing agent was not blended.

(Adhesive formulation in Comparative Example 4)
Using Dick Dry LX-703VL (manufactured by DIC Graphics: polyester polyol, non-volatile content / about 62%) as a general-purpose solvent-based laminating adhesive main agent, the curing agent is mixed as shown in Table 3, and the adhesive is used. Obtained.

(Adhesive lamination and multilayer film production methods)
The liquid obtained according to the mixing | blending of Table 2 and Table 3 was stirred, and the uniform adhesive liquid was produced. This was coated on a PET film having a thickness of 12 μm with a bar coater # 8, and then the solvent was volatilized with hot air at 80 ° C. with a dryer. Thereafter, a multilayer film of PET / adhesive / CPP was obtained by laminating with a CPP film having a thickness of 70 μm.
Next, the composite film was aged at 40 ° C. for 3 days, and the adhesive was cured to obtain a laminated film.

[Evaluation method 1, oxygen permeability]
The film obtained in various examples and comparative examples and the untreated film used for coating were in accordance with JIS-K7126 (isobaric method) using an oxygen permeability measuring device OX-TRAN2 / 21MH manufactured by Mocon, The measurement was performed under an atmosphere of 23 ° C. and 90% RH. RH indicates humidity.
In addition, the measured value on these conditions of the PET film used by each Example and the comparative example was 100 cc / m < ² > * day * atm. In addition, the CPP film exceeded the measurement range of 400 cc / m ² · day · atm in this measuring apparatus and did not substantially have an oxygen barrier function.

[Evaluation Method 2, Laminate Strength Measurement]
The laminated film for gas barrier that has been aged is cut to a width of 15 mm in parallel with the coating direction, and the ambient temperature of 25 ° C. is used between the PET film and the CPP film using an orientec Tensilon universal testing machine. The peeling rate was set to 300 mm / min, and the tensile strength when peeled by the 180 ° peeling method was defined as the adhesive strength. The unit of adhesive strength was N / 15 mm. At this time, when the adhesive strength was sufficiently strong and the PET film was ruptured, it was indicated as PET rupture.

(Materials used)
The materials used in the above Examples and Comparative Examples are as follows.
<General-purpose adhesive>
Curing agent D-110N: “Takenate D-110N” manufactured by Mitsui Chemicals, Inc. (trimethylolpropane adduct of metaxylylene diisocyanate, nonvolatile component 75.0%, NCO% 11.5%, solvent ethyl acetate)
PET film: “E-5102” manufactured by Toyobo Co., Ltd.
CPP film: “ZK93KM” manufactured by Toray Industries, Inc.

Table 2 shows the evaluation results of the adhesive in the multilayer film obtained in each example, and Table 3 shows the evaluation results in the comparative example.

As described above, the resin compositions of the present invention of Examples 1 to 5 were excellent in solubility in 2-butanone, which is a general-purpose solvent, and the adhesives prototyped using this resin composition had low oxygen permeability. That is, an adhesive having a gas barrier function and having an oxygen barrier function and excellent laminate strength could be obtained. On the other hand, the resin compositions deviating from the resin composition of the present invention had low solubility in 2-butanone in Comparative Examples 1 and 3, and could not be used as a dry laminate type adhesive.
Further, the resin composition of Comparative Example 2 had good solvent solubility and adhesive strength, but had a high oxygen permeability, that is, a poor oxygen barrier function. In addition, the film using the general-purpose adhesive of Comparative Example 4 had good adhesive strength, but the oxygen permeability was a value close to that of the PET film, resulting in substantially no oxygen barrier function.

  Since the adhesive of the present invention has gas barrier properties, it is used for electronic materials such as adhesives for protective films for solar cells and adhesives for gas barrier substrates for display elements, in addition to adhesives for film laminates for packaging materials. Any application that requires gas barrier properties, such as an adhesive, an adhesive for building materials, and an adhesive for industrial materials, can be suitably used.

Claims (9)

At least one dicarboxylic acid selected from the group consisting of isophthalic acid, orthophthalic acid, and phthalic anhydride, an aliphatic dicarboxylic acid having 3 to 5 carbon atoms , an aliphatic diol having 2 to 4 carbon atoms, and 2 to 2 carbon atoms A gas barrier material adhesive using a resin composition containing a polyamide polyester obtained by polycondensation of amino alcohol 4 and an isocyanate compound. The adhesive for gas barrier materials according to claim 1, wherein the aliphatic dicarboxylic acid having 3 to 5 carbon atoms is succinic acid . The adhesive for gas barrier materials according to claim 1 or 2, wherein the aliphatic diol having 2 to 4 carbon atoms is ethylene glycol . The adhesive for gas barrier materials according to any one of claims 1 to 3, wherein the amino alcohol having 2 to 4 carbon atoms is 2-aminoethyl alcohol . The adhesive for a gas barrier material according to any one of claims 1 to 4 , wherein the isocyanate compound contains a polyisocyanate having an aromatic ring . The adhesive for gas barrier materials according to claim 5 , wherein the polyisocyanate having an aromatic ring is metaxylene diisocyanate or a reaction product of metaxylene diisocyanate and an alcohol having two or more hydroxyl groups . It is an object for dry lamination, The adhesive for gas barrier materials in any one of Claims 1-6. The multilayer film which has the adhesive agent for gas barrier materials in any one of Claims 1-7 as an adhesive bond layer. A packaging material using the multilayer film according to claim 8 .